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US20180370288A1 - Composite materials consisting of an oriented stacking of hard-soft mixtures for mechanical coupling in the production of tire treads - Google Patents

Composite materials consisting of an oriented stacking of hard-soft mixtures for mechanical coupling in the production of tire treads Download PDF

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Publication number
US20180370288A1
US20180370288A1 US16/065,346 US201616065346A US2018370288A1 US 20180370288 A1 US20180370288 A1 US 20180370288A1 US 201616065346 A US201616065346 A US 201616065346A US 2018370288 A1 US2018370288 A1 US 2018370288A1
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US
United States
Prior art keywords
composition
stiffness modulus
modulus
tread according
tread
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
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US16/065,346
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English (en)
Inventor
Jose-Carlos ARAUJO DA SILVA
Masayuki Maesaka
Philippe Mansuy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Michelin Recherche et Technique SA Switzerland
Compagnie Generale des Etablissements Michelin SCA
Original Assignee
Michelin Recherche et Technique SA Switzerland
Compagnie Generale des Etablissements Michelin SCA
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Publication of US20180370288A1 publication Critical patent/US20180370288A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • B60C11/0041—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • B60C11/03—Tread patterns
    • B60C11/0302—Tread patterns directional pattern, i.e. with main rolling direction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
    • B60C2011/0016—Physical properties or dimensions
    • B60C2011/0025—Modulus or tan delta

Definitions

  • the present invention relates to materials making it possible to generate mechanical coupling in elastomeric compositions, of use especially for the manufacture of tyre treads.
  • tyres are essentially used on ore or coal extraction sites, and also in quarries.
  • the use consists of:
  • the tyres fitted to the mining dumpers in question are, as a general rule, fitted on the front axle of the vehicle for the first third of their life, then changed around and fitted as part of a twinned pair to the rear axle for the remaining two thirds of their life.
  • the driving torque is transmitted via the rear axle, and the braking torque is also virtually exclusively transmitted via the rear axle, using engine braking (thermal or electrical in the case of a transmission of this kind).
  • the present invention relates to a novel formulation for tyres, making it possible to significantly improve their wear resistance.
  • the tread in accordance with the invention may either be in the uncured state (before crosslinking or vulcanization) or in the cured state (after crosslinking or vulcanization). It may be in the form of a semi-finished product which may be used in a tyre or on a retreaded carcass, or else be already arranged on a tyre or tyre casing.
  • part by weight per hundred parts by weight of elastomer (or phr) should be understood as meaning, for the purposes of the present invention, the share by weight per hundred parts by weight of elastomer or rubber.
  • any range of values denoted by the expression “between a and b” represents the range of values extending from more than a to less than b (that is to say, limits a and b excluded), while any range of values denoted by the expression “from a to b” means the range of values extending from a up to b (that is to say, including the strict limits a and b).
  • the range represented by the expression “between a and b” is also and preferentially denoted.
  • composition “based on” is understood to mean a composition comprising the mixture and/or the reaction product of the various constituents used, some of these base constituents being capable of reacting or intended to react with one another, at least in part, during the various phases of manufacture of the composition, in particular during the crosslinking or vulcanization thereof.
  • a composition based on an elastomeric matrix and on sulfur comprises the elastomeric matrix and the sulfur before curing, whereas, after curing, the sulfur is no longer detectable as the latter has reacted with the elastomeric matrix with the formation of disulfide bridges.
  • the expression “predominantly comprises” is understood to mean comprises more than 50%. This may, for example, be more than 60%, 70%, 80%, 90%, or even 100%.
  • the circumferential direction also referred to as the longitudinal direction
  • the axis of rotation of the tyre is the axis about which it turns in normal use.
  • the transverse direction also referred to as the lateral direction
  • the radial direction is a direction that intersects the axis of rotation of the tyre and is perpendicular thereto.
  • X is a direction parallel to the circumferential direction
  • Y is a direction parallel to the transverse direction
  • Z is a direction parallel to the radial direction.
  • the directions XYZ form an orthogonal frame of reference ( FIG. 1 ).
  • Fx is intended to mean the horizontal component of the ground forces on the tyre in the running direction of the tyre. Reference is made to driving torque when a positive force Fx is applied, and braking torque when a negative force Fx is applied.
  • Fy is intended to mean the horizontal component of the ground forces on the tyre in the transverse direction of the tyre.
  • Fz is the vertical component.
  • Level of coupling is intended to mean the ratio of the horizontal component Fx of the ground forces on the tyre (or ground forces on the test specimen) to the vertical component Fz of the ground forces on the tyre (or ground forces on the test specimen).
  • a radial plane “YZ”, also referred to as meridian plane, is a plane which contains the axis of rotation of the tyre.
  • a circumferential plane “XZ” is a plane perpendicular to the axis of rotation of the tyre.
  • the circumferential median plane, also referred to as the equatorial plane, is a plane which is perpendicular to the axis of rotation of the tyre and which divides the tyre into two halves.
  • tread pattern is intended to mean a more or less complex system of elements in relief, separated from one another by cutouts.
  • the elements in relief of a tread pattern may be ribs or tread blocks.
  • “Rib” is intended to mean an element in relief formed on a tread and extending essentially along the circumferential direction, this element being delimited either by two cutouts or by a cutout and an edge of the tread.
  • a rib comprises two lateral walls and a contact face, the latter being intended to come into contact with the road surface during running. This element extends in the circumferential direction and encircles the tyre (legend ( 2 ) of FIG. 1 ).
  • Thread block is intended to mean an element in relief formed on a tread, this element being delimited by one or more rectilinear, curved or circular, cutouts, and optionally by an edge of the tread.
  • a tread block also comprises a contact face, the latter being intended to come into contact with the road surface during running (legend ( 3 ) of FIG. 1 ).
  • the cutouts may either be grooves or sipes, depending on their thickness, that is to say the distance between the walls of material delimiting them, and their function during running.
  • the thickness of a groove is typically at least equal to 1 mm, whereas the thickness of a sipe is typically at most equal to 1 mm.
  • a “cutout” denotes a groove and corresponds to the space delimited by walls of material facing one another and spaced apart from one another by a non-zero distance, preferably a distance greater than 1 mm, for example greater than 2, 3, 4 or 5 mm (legends ( 4 ) and ( 5 ) of FIG. 1 ).
  • the carbon-based products mentioned in the description may be of fossil or biobased origin. In the latter case, they may partially or completely result from biomass or be obtained from renewable starting materials resulting from biomass.
  • the tread consists of a plurality of layers comprising layers formed by a composition having a low stiffness modulus.
  • composition having a low stiffness modulus is intended to mean a composition, the modulus of extension at 5% deformation of which is within a range extending from 2 to 8 MPa.
  • the modulus of extension at 5% deformation of the composition having a low stiffness modulus is within a range extending from 3 to 6 MPa.
  • composition having a low stiffness modulus may advantageously be an elastomeric composition based on an elastomeric matrix, at least one reinforcing filler and at least one crosslinking system.
  • any elastomeric matrix known to those skilled in the art for the manufacture of treads may be used in the composition having a low stiffness modulus of the tread pattern of the tread according to the invention.
  • the elastomeric matrix may comprise a diene elastomer, preferably an elastomer selected from isoprene elastomers, butadiene and styrene copolymers, polybutadienes and mixtures thereof.
  • iene elastomer should be understood, in a known way, as meaning an (one or more is understood) elastomer resulting at least in part (i.e., a homopolymer or a copolymer) from diene monomers (monomers bearing two conjugated or non-conjugated carbon-carbon double bonds).
  • diene elastomers are well known to those skilled in the art and can be classified into two categories; “essentially unsaturated” or “essentially saturated”. “Essentially unsaturated” is understood to mean generally a diene elastomer resulting at least in part from conjugated diene monomers having a content of units of diene origin (conjugated dienes) which is greater than 15% (mol %); thus, diene elastomers such as butyl rubbers or copolymers of dienes and of ⁇ -olefins of EPDM type do not fall under the preceding definition and may especially be described as “essentially saturated” diene elastomers (low or very low content, always less than 15%, of units of diene origin).
  • “highly unsaturated” diene elastomer is understood in particular to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
  • Diene elastomer capable of being used in the compositions in accordance with the invention is understood more particularly to mean:
  • diene elastomer any type of diene elastomer
  • those skilled in the art of tyres will understand that the present invention is preferably employed with essentially unsaturated diene elastomers, in particular of the type (a) or (b) above.
  • the latter contain from 20% to 99% by weight of diene units and from 1% to 80% by weight of vinylaromatic units.
  • conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C 1 -C 5 alkyl)-1,3-butadienes, such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene or 2-methyl-3-isopropyl-1,3-butadiene, an aryl-1,3-butadiene, 1,3-pentadiene or 2,4-hexadiene.
  • 1,3-butadiene 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C 1 -C 5 alkyl)-1,3-butadienes, such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-but
  • vinylaromatic compounds styrene, ortho-, meta- or para-methylstyrene, the “vinyltoluene” commercial mixture, para-(tert-butyl)styrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene or vinylnaphthalene.
  • Isoprene elastomer is understood to mean, in a known way, an isoprene homopolymer or copolymer, in other words a diene elastomer selected from the group consisting of natural rubber (NR), synthetic polyisoprenes (IRs), various isoprene copolymers and the mixtures of these elastomers.
  • NR natural rubber
  • IRs synthetic polyisoprenes
  • various isoprene copolymers and the mixtures of these elastomers.
  • isoprene copolymers of isobutene/isoprene (butyl rubber—IIR), isoprene/styrene (SIR), isoprene/butadiene (BIR) or isoprene/butadiene/styrene (SBIR) copolymers.
  • This isoprene elastomer is preferably natural rubber or a synthetic cis-1,4-polyisoprene, preferably natural rubber.
  • the synthetic polyisoprene can be a polyisoprene having a content (mol %) of cis-1,4- bonds of greater than 90%, more preferentially still of greater than 98%.
  • the elastomers used in the context of the present invention can, for example, be block, random, sequential or microsequential elastomers and can be prepared in dispersion or in solution; they can be coupled and/or star-branched and/or functionalized with a coupling and/or star-branching and/or functionalization agent.
  • the isoprene elastomer can be selected from the group consisting of natural rubber, synthetic polyisoprene and their mixture.
  • the isoprene elastomer is natural rubber.
  • copolymer of butadiene units and of styrene units refers to any copolymer obtained by copolymerization of one or more butadiene(s) with one or more styrene compounds.
  • styrene compounds styrene, ortho-, meta- or para-methylstyrene, the “vinyltoluene” commercial mixture, para-(tert-butyl)styrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene or vinylnaphthalene.
  • elastomers can have any microstructure, which depends on the polymerization conditions used, especially on the presence or absence of a modifying and/or randomizing agent and on the amounts of modifying and/or randomizing agent employed.
  • the elastomers can, for example, be block, random, sequential or microsequential elastomers and can be prepared in dispersion or in solution.
  • the butadiene and styrene copolymer can, for example, be butadiene/styrene copolymer (SBR). It can, for example, concern an SBR prepared in emulsion (“ESBR”) or an SBR prepared in solution (“SSBR”).
  • SBR butadiene/styrene copolymer
  • ESBR emulsion
  • SSBR SBR prepared in solution
  • the contents of vinyl (1,2-), trans-1,4- and cis-1,4- bonds of the butadiene part of the SBR can be variable.
  • the vinyl content can be between 15% and 80% (mol %) and the content of trans-1,4- bonds between 15% and 80% (mol %).
  • the diene elastomer can also predominantly, indeed even exclusively, comprise a polybutadiene.
  • polybutadienes and in particular those having a content (mol %) of 1,2- units of between 4% and 80% or those having a content (mol %) of cis-1,4- units of greater than 80%, polyisoprenes, butadiene/styrene copolymers and in particular those having a Tg (glass transition temperature Tg, measured according to ASTM D3418) of between 0° C. and ⁇ 70° C. and more particularly between ⁇ 10° C.
  • Tg glass transition temperature Tg, measured according to ASTM D3418
  • butadiene/styrene/isoprene copolymers those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, an isoprene content of between 15% and 60% by weight and more particularly of between 20% and 50%, a butadiene content of between 5% and 50% by weight and more particularly of between 20% and 40%, a content (mol %) of 1,2- units of the butadiene part of between 4% and 85%, a content (mol %) of trans-1,4- units of the butadiene part of between 6% and 80%, a content (mol %) of 1,2- plus 3,4- units of the isoprene part of between 5% and 70% and a content (mol %) of trans-1,4- units of the isoprene part of between 10% and 50%, and more generally any butadiene/styrene/isoprene copolymer having a Tg of between ⁇ 5° C. and ⁇ 70°
  • the crosslinking system of the composition having a low stiffness modulus can be based on sulfur and/or on sulfur donors and/or on peroxide and/or on bismaleimides.
  • the crosslinking system is preferentially a vulcanization system, i.e. a system based on sulfur (and/or on a sulfur-donating agent) and on a primary vulcanization accelerator.
  • various known secondary vulcanization accelerators or vulcanization activators are added, such as zinc oxide, stearic acid or equivalent compounds, or guanidine derivatives (in particular diphenylguanidine), or else known vulcanization retarders, which are incorporated during the first non-productive phase and/or during the productive phase, as described subsequently.
  • the crosslinking system preferably sulfur, may be used at a preferential content of between 0.1 and 5 phr, in particular between 0.1 and 2 phr, further preferably between 0.5 and 1.5 phr.
  • the reinforcing filler is known for its abilities to reinforce a rubber composition which can be used in the manufacture of tyres.
  • the reinforcing filler of the composition having a low stiffness modulus can comprise carbon black, an organic filler other than carbon black, an inorganic filler or the mixture of at least two of these fillers.
  • the reinforcing filler can predominantly comprise, indeed even exclusively comprise, carbon black.
  • the reinforcing filler can also predominantly comprise, indeed even exclusively comprise, a reinforcing inorganic filler.
  • Such a reinforcing filler typically consists of nanoparticles, the (weight-)average size of which is less than a micrometre, generally less than 500 nm, most commonly between 20 and 200 nm, in particular and more preferentially between 20 and 150 nm.
  • the carbon black has a BET specific surface area preferably of at least 90 m 2 /g, more preferentially of at least 100 m 2 /g.
  • the blacks conventionally used in tyres or their treads (“tyre-grade” blacks) are suitable in this regard. Among the latter, mention will more particularly be made of the reinforcing carbon blacks of the 100, 200 and 300 series, or the blacks of the 500, 600 or 700 series (ASTM grades), such as, for example, the N115, N134, N234, N326, N330, N339, N347, N375, N550, N683 and N772 blacks.
  • carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as support for some of the rubber additives used.
  • the carbon blacks might, for example, be already incorporated in the diene elastomer, especially isoprene elastomer, in the form of a masterbatch (see, for example, Applications WO 97/36724 and WO 99/16600).
  • the BET specific surface area of the carbon blacks is measured according to Standard D6556-10 [multipoint (at least 5 points) method—gas: nitrogen—relative pressure p/p 0 range: 0.1 to 0.3].
  • organic fillers other than carbon blacks Mention may be made, as examples of organic fillers other than carbon blacks, of functionalized polyvinyl organic fillers, such as described in Applications WO 2006/069792, WO 2006/069793, WO 2008/003434 and WO 2008/003435.
  • ⁇ inorganic filler should be understood here to mean any inorganic or mineral filler, regardless of its colour and its origin (natural or synthetic), also known as “white filler”, “clear filler” or even “non-black filler”, in contrast to carbon black, capable of reinforcing, by itself alone, without means other than an intermediate coupling agent, a rubber composition intended for the manufacture of pneumatic tyres, in other words capable of replacing, in its reinforcing role, a conventional tyre-grade carbon black; such a filler is generally characterized, in a known way, by the presence of hydroxyl (—OH) groups at its surface.
  • —OH hydroxyl
  • Mineral fillers of the siliceous type are especially suitable as reinforcing inorganic fillers.
  • the silica used can be any reinforcing silica known to those skilled in the art, especially any precipitated or fumed silica exhibiting a BET surface area and also a CTAB specific surface area both of less than 450 m 2 /g, preferably from 30 to 400 m 2 /g, especially between 60 and 300 m 2 /g.
  • HDSs highly dispersible precipitated silicas
  • Ultrasil 7000 and Ultrasil 7005 silicas from Degussa the Zeosil 1165MP, 1135MP and 1115MP silicas from Rhodia
  • Hi-Sil EZ150G silica from PPG
  • Zeopol 8715, 8745 and 8755 silicas from Huber or the silicas with a high specific surface area as described in Application WO 03/016387.
  • the BET specific surface area is determined in a known way by gas adsorption using the Brunauer-Emmett-Teller method described in The Journal of the American Chemical Society, Vol. 60, page 309, February 1938, more specifically according to French Standard NF ISO 9277 of December 1996 (multipoint (5 point) volumetric method—gas: nitrogen—degassing: 1 hour at 160° C.—relative pressure p/p 0 range: 0.05 to 0.17).
  • the CTAB specific surface area is the external surface area determined according to French Standard NFT 45-007 of November 1987 (method B).
  • Mineral fillers of the aluminous type in particular alumina (Al 2 O 3 ) or aluminum (oxide) hydroxides, or else reinforcing titanium oxides, for example described in U.S. Pat. No. 6,610,261 and U.S. Pat. No. 6,747,087, are also suitable as reinforcing inorganic fillers.
  • the physical state in which the reinforcing inorganic filler is provided is not important, whether it is in the form of a powder, of microbeads, of granules, of beads or any other appropriate densified form.
  • the term “reinforcing inorganic filler” is also understood to mean mixtures of different reinforcing inorganic fillers, in particular of highly dispersible siliceous and/or aluminous fillers as described above.
  • an at least bifunctional coupling agent intended to provide a satisfactory connection, of chemical and/or physical nature, between the inorganic filler (surface of its particles) and the diene elastomer.
  • Use is made in particular of organosilanes or polyorganosiloxanes which are at least bifunctional.
  • the content of coupling agent is advantageously less than 12 phr, it being understood that it is generally desirable to use as little as possible of it.
  • the content of coupling agent represents from 0.5% to 15% by weight relative to the amount of inorganic filler. Its content is preferentially between 0.5 and 9 phr, more preferentially within a range extending from 3 to 9 phr. This content is easily adjusted by those skilled in the art depending on the content of inorganic filler used in the composition.
  • the content of reinforcing filler may be within a range extending from 10 to 160 phr, preferably from 10 to 150 phr, preferably from 10 to 90 phr, preferably from 20 to 70 phr, preferably from 25 to 60 phr.
  • the content of reinforcing filler is within a range extending from 10 to 30% of the fraction by volume, preferably from 15 to 25% of the fraction by volume, relative to the volume of the composition having a low stiffness modulus.
  • composition having a low stiffness modulus may also comprise all or a portion of the usual additives customarily used in elastomer compositions intended to constitute treads, such as, for example, plasticizers, fibres, pigments, protective agents, such as antiozone waxes, chemical antiozonants, antioxidants, or antifatigue agents, well known to those skilled in the art.
  • additives customarily used in elastomer compositions intended to constitute treads such as, for example, plasticizers, fibres, pigments, protective agents, such as antiozone waxes, chemical antiozonants, antioxidants, or antifatigue agents, well known to those skilled in the art.
  • the composition having a low stiffness modulus does not comprise reinforcing resin and/or reinforcing fibres.
  • the tread consists of a plurality of layers comprising layers formed by a composition having a high stiffness modulus.
  • composition having a high stiffness modulus is intended to mean a composition, the modulus of extension at 5% deformation of which is within a range extending from 30 MPa to 50 GPa.
  • the modulus of extension at 5% deformation of the composition having a high stiffness modulus is within a range extending from 30 to 300 MPa, preferably from 40 to 200 MPa.
  • those skilled in the art can measure the stiffness, the modulus of extension at 5% deformation of which according to a method based on standard NF ISO 37 of December 2005 on a type 2 dumbbell test specimen and measure the elastic modulus at 5% deformation at 23° C.
  • compositions having a high stiffness modulus have several means at their disposal in order to obtain a composition having a high stiffness modulus.
  • those skilled in the art may use high contents of reinforcing filler and/or crosslinking system and/or reinforcing fibres, for example in an elastomeric matrix. They may also, alternatively or additionally, use thermoplastic materials or thermoplastic elastomers.
  • the composition having a high stiffness modulus may be an elastomeric composition based on an elastomeric matrix, at least one reinforcing filler and at least one crosslinking system.
  • the composition having a high stiffness modulus may also be a thermoplastic or comprise a thermoplastic elastomer.
  • composition having a high stiffness modulus is an elastomeric composition based on an elastomeric matrix
  • at least one reinforcing filler and at least one crosslinking system may be identical to those of the composition having a low stiffness modulus.
  • the elastomeric matrix, the reinforcing filler and the crosslinking system may be identical to those of the composition having a low stiffness modulus.
  • the content of reinforcing filler of the composition having a high stiffness modulus may generally be within a range extending from 10 to 160 phr, preferably from 10 to 150 phr, preferably from 10 to 90 phr, preferably from 20 to 70 phr, preferably from 25 to 60 phr.
  • the content of reinforcing filler of the composition having a high stiffness modulus is within a range extending from 1 to 50% of the fraction by volume, preferably from 10 to 40%, preferably from 15 to 25% of the fraction by volume, relative to the volume of the composition having a high stiffness modulus.
  • the content of reinforcing filler may be within a range extending from 25 to 50% of the fraction by volume, preferably from 40 to 50% of the fraction by volume, relative to the volume of the composition having a high stiffness modulus.
  • the crosslinking system of the composition having a high stiffness modulus preferably sulfur
  • the content of crosslinking system may be between 20 and 40 phr, preferably between 30 and 40 phr.
  • the composition having a high stiffness modulus may comprise a reinforcing resin.
  • the reinforcing resin may for example be a resin selected from polyepoxide resins, melamine/formaldehyde resins, phenol/formaldehyde resins, urea/formaldehyde resins, polyurethane resins, unsaturated polyester resins, vinyl ester resins, polyimide resins, diallyl phthalate resins, allyl diglycol carbonate resins and polyorganosiloxane resins, preferably from phenol/formaldehyde resins or epoxy resins, the latter being especially able to be used as adhesion primer.
  • the reinforcing resin may be a resin selected from melamine/formaldehyde resin, phenol/formaldehyde resin or urea/formaldehyde resin, and even more preferentially phenol/formaldehyde resin.
  • the reinforcing resin may contain an activator which enables the crosslinking of the resin.
  • the activator may be selected from hexamethylenetetramine (HMTA) with, especially, Technic-SCH from Techno Waxchem Pvt. Ltd. ThuB, India, or hexa(methoxymethyl)melamine (H3M), with, especially, Cyrez CRA100 from Allnex, 1070 Anderlecht—Brussels, Belgium.
  • HMTA hexamethylenetetramine
  • H3M hexa(methoxymethyl)melamine
  • the composition having a high stiffness modulus may be a thermoplastic.
  • the thermoplastic preferentially has a melting or softening point of greater than 100° C., preferentially greater than 140° C. and very preferentially of between 170 and 300° C.
  • the softening point may be measured, for example, according to the method described in standard ASTM D 1525.
  • the thermoplastic is selected from the group consisting of polyolefins, vinyl chloride polymers, polystyrenes, polyamides, polyesters, ethylene/vinyl alcohol (EVOH) copolymers, polyacrylates, polyacetals and mixtures thereof.
  • EVOH ethylene/vinyl alcohol
  • the polyolefins are selected from polyethylenes and polypropylenes.
  • the vinyl chloride polymers are selected from polyvinyl chlorides (PVCs), polyvinylidene chlorides (PVDCs), chlorinated polyvinyl chlorides (CPVCs), and mixtures thereof.
  • PVCs polyvinyl chlorides
  • PVDCs polyvinylidene chlorides
  • CPVCs chlorinated polyvinyl chlorides
  • the polyesters are selected from polyethylene terephthalates (PETs), polybutylene terephthalates (PBTs), polycarbonates (PCs) and polyethylene naphthalates (PENs), and mixtures thereof.
  • PETs polyethylene terephthalates
  • PBTs polybutylene terephthalates
  • PCs polycarbonates
  • PENs polyethylene naphthalates
  • the polyamides may be selected from aliphatic polyamides and preferably from polyamides 6, polyamides 6-6, polyamides 11, and mixtures thereof.
  • polyacrylate is polymethyl methacrylate (PMMA); an example of polyacetal is polyoxymethylene (POM).
  • PMMA polymethyl methacrylate
  • POM polyoxymethylene
  • thermoplastics are commercially available, sold for example, as regards the polyamides, as PA11 Rilsan from Arkema, PA12 Grilamid from EMS-Grimory, PA6 Trogamid from Evonik, PA12 Orgasol from Arkema. They have for example been described, along with their synthesis, in the documents “Techniques de l' publication” [ The Engineer's Techniques ], ref A3360 and 0702 polyamides PA, which reference originates from “matáriaux Explos et composites” [ Plastic and composite materials ] by B. Guerin.
  • the thermoplastic may be rendered adhesive, that is to say treated so as to improve the adhesion thereof to the layers comprising a composition having a low stiffness modulus.
  • the thermoplastic may be rendered adhesive with an adhesive selected from epoxy adhesives, followed by a treatment with liquid resorcinol/formaldehyde latex (RFL), and formaldehyde-based adhesives, preferably RFL adhesives.
  • RFL adhesive of use for rendering the thermoplastic adhesive mention may be made of those described in application WO 2001/057116.
  • the composition having a high stiffness modulus may comprise a thermoplastic elastomer (TPE).
  • TPE thermoplastic elastomer
  • the composition having a high stiffness modulus comprises at least, as sole elastomer or predominant elastomer by weight, a thermoplastic elastomer.
  • TPEs have a structure intermediate between thermoplastic polymers and elastomers. They consist of rigid thermoplastic sequences connected by flexible elastomer sequences, for example polybutadiene, polyisoprene, poly(ethylene/butylene) or else polyisobutylene. They are often triblock elastomers with two rigid segments connected by a flexible segment. The rigid and flexible segments can be positioned linearly, in a star or branched configuration. Typically, each of these segments or blocks contains at least more than 5, generally more than 10, base units (for example, styrene units and isoprene units for a styrene/isoprene/styrene triblock copolymer).
  • thermoplastic elastomer may be selected from the group consisting of thermoplastic styrene elastomers (TPSs), polyether block amide (PEBA) copolymers, copolyesters (COPEs), thermoplastic polyurethane elastomers (TPUs), vulcanized thermoplastics (TPVs), thermoplastic polyolefins (TPOs) and the mixture of these TPEs.
  • TPSs thermoplastic styrene elastomers
  • PEBA polyether block amide
  • COPEs copolyesters
  • TPUs thermoplastic polyurethane elastomers
  • TPVs vulcanized thermoplastics
  • TPOs thermoplastic polyolefins
  • the thermoplastic elastomer is a TPS elastomer.
  • TPS elastomer As example of TPS elastomer, mention may be made of the following copolymers: styrene/butadiene/styrene (SBS), styrene/isoprene/styrene (SIS), styrene/ethylene/butylene/styrene (SEBS), styrene/isoprene/butylene/styrene (SIBS), styrene/ethylene/propylene/styrene (SEPS) and ii) less than 90% by weight, preferably from 0% to 80% of one or more diblock copolymers of styrene/butadiene (SB) or styrene/isoprene (SI) or styrene/ethylene/butylene (SEB) or styrene/isoprene/butylene (SIB) or styrene/ethylene/
  • the glass transition temperature (Tg, measured according to ASTM D3418) of the elastomeric block of the TPE elastomer is preferred to be less than ⁇ 20° C., more preferentially less than ⁇ 40° C.
  • the number-average molecular weight (denoted by Mn) of the TPE elastomer is preferentially between 30 000 and 500 000 g/mol, more preferentially between 40 000 and 400 000 g/mol.
  • the number-average molecular weight (Mn) of the TPS elastomer is determined, in a known way, by size exclusion chromatography (SEC). The sample is dissolved beforehand in tetrahydrofuran at a concentration of approximately 1 g/l and then the solution is filtered through a filter with a porosity of 0.45 ⁇ m before injection.
  • the apparatus used is a Waters Alliance chromatographic line.
  • the elution solvent is tetrahydrofuran, the flow rate is 0.7 ml/min, the temperature of the system is 35° C. and the analytical time is 90 min.
  • the injected volume of the solution of the polymer sample is 100 ⁇ l.
  • the detector is a Waters 2410 differential refractometer and its associated software, for making use of the chromatographic data, is the Waters Millennium system.
  • the calculated average molar masses are relative to a calibration curve produced with polystyrene standards.
  • the TPE elastomer may be the sole elastomer of the composition having a high stiffness modulus, or else be combined with other elastomers.
  • the TPE elastomer constitutes the predominant elastomer by weight.
  • additional elastomers minor by weight, could for example be diene elastomers such as natural rubber or a synthetic polyisoprene, a butyl rubber or thermoplastic elastomers other than styrene elastomers, as long as their microstructures are compatible.
  • the elastomer other than the thermoplastic elastomer is selected from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and the mixtures of these elastomers.
  • the composition having a high stiffness modulus may comprise from 50 to less than 100 phr, preferably from 70 to less than 100 phr, preferably from 80 to less than 100 phr, preferably from 90 to less than 100 phr, of TPE.
  • the composition having a high stiffness modulus comprises from more than 0 to 50 phr, preferably from more than 0 to 30 phr, preferably from more than 0 to 20 phr, preferably from 0 to 10 phr, of another elastomer other than the TPE.
  • thermoplastic elastomer is the sole thermoplastic elastomer, advantageously the sole elastomer, present in the composition having a high stiffness modulus.
  • the composition having a high stiffness modulus comprises exclusively, that is to say 100 phr of, TPE.
  • the TPE elastomers may be processed in the conventional way, by extrusion or moulding, for example using a starting material available in the form of beads or granules.
  • the TPE elastomers are commercially available, sold for example, as regards the SIBSs, by Kaneka under the name Sibstar (e.g. Sibstar 102T, Sibstar 103T or Sibstar 073T). They have, for example, been described, along with their synthesis, in the patent documents EP 731 112, U.S. Pat. No. 4,946,899 and U.S. Pat. No. 5,260,383.
  • Sibstar e.g. Sibstar 102T, Sibstar 103T or Sibstar 073T.
  • TPEs were developed, first of all, for biomedical applications and then described in various applications specific to TPEs, especially to TPS elastomers, as varied as medical equipment, parts for motor vehicles or for domestic electrical appliances, sheathing for electric wires, leaktightness parts or elastic parts (see, for example, EP 1 431 343, EP 1 561 783, EP 1 566 405 and WO 2005/103146).
  • the composition having a high stiffness modulus may comprise a reinforcing filler and a crosslinking system.
  • the reinforcing filler and/or the crosslinking system of the composition having a high stiffness modulus according to the third embodiment are identical to those of the first embodiment of the present invention.
  • the tread according to the present invention comprises a tread pattern.
  • the layers are oriented within the tread pattern parallel to a plane which is (i) perpendicular to the equatorial plane and (ii) oriented at an angle ⁇ expressed in degrees relative to the radial plane, the angle ⁇ being within a range extending from 15 to 35 degrees or from 55 to 75 degrees.
  • the orientation of the layers in the tread according to the invention is expressed relative to a tread arranged on a tyre.
  • a tread arranged on a tyre Those skilled in the art will know how to readily convert the orientation of the layers when the tread is arranged flat, for example in the form of a semi-finished article.
  • the tread In the event that the tread is arranged flat, it could be defined according to directions parallel to its length, its width and its thickness, which would correspond, respectively, to the circumferential “X”, transverse “Y” and radial “Z” directions.
  • the circumferential plane would then be a plane defined by the length and the thickness of the tread, and the radial plane would be a plane defined by the width and the thickness of the tread.
  • Those skilled in the art can measure the angle of the layers within the tread by removing a part of the tread, preferentially by removing half the width of a rib along a plane parallel to the plan XoZ, so as to make an interface appear that contains the layers, and by taking a test specimen of material by cutting the tread according to FIG. 2 , and by creating the histogram of orientation of the layers in the plane XOZ relative to the direction Z by optical reflection microscopy.
  • this orientation gives the composite material the ability to transfer a portion of the component Fz of the ground forces on the tyre to the component Fx, that is to say from the vertical component to the horizontal component in the direction of running of the tyre.
  • This level of coupling is particularly advantageous for improving the wear resistance of tyres for civil engineering vehicles, especially in their specific conditions of use.
  • the level of coupling is not the same.
  • the tread pattern will transform the component Fz into a positive component Fx.
  • the angle ⁇ is between 35 and 55 degrees, the level of coupling becomes too low, or even zero at around 45 degrees, to give the desired property to the tread pattern of the tread according to the invention.
  • the angle ⁇ is less than 15 degrees or greater than 75 degrees.
  • the plurality of layers comprises layers formed by a composition having a low stiffness modulus and layers formed by a composition having a high stiffness modulus.
  • the plurality of layers comprises at least one (that is to say one or more) group of layers formed by a composition having a low stiffness modulus and at least one (that is to say one or more) group of layers formed by a composition having a high stiffness modulus.
  • a group of layers is intended to mean one or more layers identical to one another.
  • these layers may differ from one another by the nature of the elastomeric matrix, of the thermoplastic or of the thermoplastic elastomer, the nature or the concentration of reinforcing filler, the nature or the concentration of reinforcing resin, the crosslinking system, the additives, etc.
  • the plurality of layers is formed by at least two groups of different layers, or even more, for example three, four or five groups of layers that are different from one another.
  • the plurality of layers is formed of two groups of different layers, that is to say by one group of layers formed by a composition having a low stiffness modulus and one group of layers formed by a composition having a high stiffness modulus, preferably arranged alternately.
  • any distribution of layers formed by a composition having a low stiffness modulus and layers formed by a composition having a high stiffness modulus may be implemented.
  • the layers may or may not be distributed alternately.
  • the distribution may follow the following formula:
  • the distribution may follow the following formula:
  • the total number of layers within the tread pattern is limited by the length of the tread. Those skilled in the art are able to determine this number as a function of the thickness of the layers and of their orientation within the tread pattern.
  • the tread pattern of the tread is formed by a group of layers formed by a composition having a low stiffness modulus and a group of layers formed of a composition having a high stiffness modulus, distributed alternately within the tread pattern of the tread ( FIG. 2 ).
  • the composition having a low stiffness modulus has a stiffness at extension which is at least 5 times less, preferably at least 10 times less, than that of the composition having a high stiffness modulus.
  • Those skilled in the art are able to determine how to measure the stiffness at extension of the compositions having low and high stiffness moduli. For example, they may use a method based on standard NF ISO 37 of December 2005 on a type 2 dumbbell test specimen and measure the elastic modulus at 5% deformation at 23° C.
  • the modulus E H , and the fraction by volume ⁇ H of the composition having a high modulus, and the modulus E B , and the fraction by volume ⁇ B (or 1 ⁇ H) of the composition having a low modulus are defined such that the formula
  • each of the layers formed by a composition having a low stiffness modulus may be within a range extending from 1 to 20 mm, preferably from 1 to 10 mm.
  • the thickness of each of the layers formed by a composition having a high stiffness modulus may be within a range extending from 0.1 to 20 mm, preferably from 0.1 to 10 mm.
  • the thickness of each of the layers may be within a range extending from 0.1 to 5 mm, preferably from 0.1 to 2 mm.
  • the thickness of each of the layers may be within a range extending from 0.1 to 20 mm, preferably from 0.1 to 10 mm.
  • the volume of the layers of the composition having a low stiffness modulus may represent from 50 to 95% by volume, preferably from 60 to 95% by volume, relative to the volume of the tread pattern of the tread.
  • the volume of the layers of the composition having a high stiffness modulus may represent respectively from 5 to 50% by volume, preferably from 5 to 40% by volume, relative to the volume of the tread pattern of the tread.
  • the present invention may be applied to any type of tyre.
  • another subject of the present invention is a tyre comprising a tread according to the invention.
  • a tyre comprises a tread intended to come into contact with the ground via a tread surface and connected via two sidewalls to two beads, the two beads being intended to provide a mechanical connection between the tyre and the rim on which the tyre is fitted.
  • a radial tyre more particularly comprises a reinforcement comprising a crown reinforcement radially internal to the tread and a carcass reinforcement radially internal to the crown reinforcement.
  • a tyre may be provided with a carcass reinforcement surmounted radially on the outside by a crown reinforcement in order to produce hooping of said carcass reinforcement.
  • the crown reinforcement is generally formed by a stack of a plurality of reinforcing plies, these reinforcers forming generally non-zero angles with the circumferential direction.
  • a tyre especially comprises a tread, the tread surface of which is provided with a tread pattern formed by a plurality of grooves delimiting elements in relief (tread blocks, ribs) so as to generate material edge corners and also voids.
  • These grooves represent a volume of voids which, related to the total volume of the tread (including both the volume of elements in relief and that of all the grooves), is expressed by a percentage denoted, in the present document, by “volumetric void ratio”.
  • a volumetric void ratio equal to zero indicates a tread without grooves or voids.
  • the present invention is particularly well suited to tyres intended for civil engineering vehicles and to heavy-duty vehicles, more particularly to civil engineering vehicles, the tyres of which are subjected to particularly specific stresses.
  • the tyre according to the invention is a tyre for civil engineering or heavy duty vehicles, preferably civil engineering vehicles.
  • the tread according to the invention may have one or more grooves, the mean depth of which ranges from 15 to 120 mm, preferably 65 to 120 mm.
  • the tyres according to the invention may have a diameter ranging from 20 to 63 inches, preferably from 35 to 63 inches.
  • the mean volumetric void ratio over the whole of the tread according to the invention may be within a range extending from 5 to 40%, preferably of from 5 to 25%.
  • the tread patterns of the tread may be obtained according to the process defined below.
  • the masterbatches can be manufactured in appropriate mixers, using two successive preparation phases according to a general procedure well known to those skilled in the art: a first phase of thermomechanical working or kneading (sometimes referred to as “non-productive” phase) at high temperature, up to a maximum temperature of between 130° C. and 200° C., preferably between 145° C. and 185° C., followed by a second phase of mechanical working (sometimes referred to as “productive” phase) at lower temperature, typically of less than 110° C., for example between 40° C. and 100° C., during which finishing phase the chemical crosslinking agent, in particular the crosslinking system, is incorporated.
  • a first phase of thermomechanical working or kneading sometimes referred to as “non-productive” phase
  • a second phase of mechanical working sometimes referred to as “productive” phase
  • productive phase typically of less than 110° C., for example between 40° C. and 100° C.
  • the first (non-productive) phase is carried out in a single thermomechanical step during which all the necessary constituents, the optional additional covering agents or processing aids and various other additives, with the exception of the vulcanization system, are introduced into an appropriate mixer, such as an ordinary internal mixer.
  • the total duration of the kneading, in this non-productive phase is preferably between 2 and 10 min.
  • the vulcanization system is then incorporated at low temperature, generally in an external mixer, such as an open mill; everything is then mixed (productive phase) for a few minutes, for example between 5 and 15 min.
  • the tread pattern composition thus obtained is subsequently calendered, for example in the form of a layer.
  • composition having a high stiffness modulus is an elastomeric composition based on an elastomeric matrix, at least one reinforcing filler and at least one crosslinking system, or when it comprises a thermoplastic elastomer
  • this composition may be prepared according to a process that is similar or identical to that of the composition having a low stiffness modulus.
  • the composition having a high stiffness modulus is a thermoplastic
  • it may be produced in suitable mixers according to processes that are well known to those skilled in the art.
  • the thermoplastic material generally in the form of granules, is introduced into a mixer and is worked or kneaded at a temperature above its softening point, in general at a temperature greater by 10° C. than the melting point or the glass transition temperature of the thermoplastic.
  • thermoplastic material is cooled to a temperature below its softening point, and extruded or calendered in the form of a sheet or slab which is subsequently cut so as to obtain elements on the centimetre scale of desired forms and dimensions.
  • layers of composition having low and high stiffness moduli may be assembled flat, alternately, and cut by any suitable means, for example by water jet cutting, at the desired angle, so as to form tread pattern elements that may be arranged on an uncured tyre in a manner well known to those skilled in the art.
  • FIG. 1 is a schematic depiction of a tyre ( 1 ), the tread of which comprises a rib ( 2 ) located in the central zone of the tyre ( 1 ), and tread blocks ( 3 ), the rib and the tread blocks being separated by circumferential grooves ( 4 ) and substantially transverse grooves ( 5 ).
  • FIG. 2 is a schematic depiction of several embodiments of a tread pattern according to the invention, viewed in section along the plane XZ.
  • This tread pattern is composed of a plurality of layers (c 1 ) formed of a composition having a high stiffness modulus (thinner) and of layers (c 2 ) formed of a composition having a low stiffness modulus (thicker), which are parallel and adjacent to one another and are oriented parallel to a plane which is (i) perpendicular to the plane XZ and (ii) oriented at an angle (a) of 20 degrees for E1 and E3, of 25 degrees for E4 and of 30 degrees for E2, relative to the plane YZ.
  • composition A which is a composition having a low stiffness modulus
  • composition B which is a composition having a high stiffness modulus
  • a B NR 100 100 Silica (2) 15 Carbon black (3) 40 Carbon black (4) 75 ZnO (5) 3 8 Stearic acid 1 1 PEG (6) 2.5 FP resin (7) 11 HTT3H (8) 3 H3M72 (9) 6 Sulfur 2 5 Accelerator (10) 1.7 Accelerator (11) 1 Antioxidant (12) 1 1.5 Modulus of extension (a) 4.7 MPa 54 MPa (1) Natural rubber (2) Ultrasil VN3, sold by Evonik (3) Carbon black of N234 grade according to Standard ASTM D-1765 (4) Carbon black of N330 grade according to Standard ASTM D-1765 (5) Zinc oxide of industrial grade from Umicore (6) Polyethylene glycol with an Mn of 6000-20 000 g/mol, sold by Sasol Marl (7) Phenol/formaldehyde resin (8) Hexamethylenetetramine hardener (9) Hexa(methoxymethyl)melamine hardener (10) N-cyclohexyl-2-benzothiazolesulfenamide, Santocure
  • Samples E1, E2, E3 and E4 were produced from compositions A and B in the form of layers arranged alternately and parallel to a plane defined by (i) the direction Y and (ii) a straight line oriented at 20, 25 or 30 degrees relative to the direction Z in a plane defined by the directions X and Z.
  • a control sample R1 was produced solely with a composition A, without using oriented layers.
  • a force Fz of 900 daN, corresponding to a mean pressure of 9 bar, or of 600 daN, corresponding to a mean pressure of 6 bar was applied to the surface of the samples using an electric actuating cylinder and the resulting force Fx was measured using a force sensor.
  • the ratio of Fx divided by Fz is referred to as the level of coupling and is measured at two different mean pressures.
  • composition C (having a high stiffness modulus) made of a thermoplastic material, namely a polyamide 66 rendered adhesive with an RFL adhesive.
  • the layers made of composition A were 2 mm thick and those of composition C were 1 mm thick. The fraction by volume of the composition C was therefore 33% relative to the volume of the test specimen.
  • compositions A and C were arranged alternately and oriented parallel to a plane defined by (i) the direction Y and (ii) a straight line oriented at 25 or 45 degrees relative to the direction Z in a plane defined by the directions X and Z.
  • the present invention therefore provides treads making it possible to transfer a proportion of the ground forces on the tyre from the component Fz into different components Fx, making it possible to effectively improve the wear resistance of the tyres. These results are particularly beneficial for vehicles running on non-bituminous ground, such as the majority of civil engineering vehicles and some heavy-duty vehicles.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
US16/065,346 2015-12-22 2016-12-15 Composite materials consisting of an oriented stacking of hard-soft mixtures for mechanical coupling in the production of tire treads Abandoned US20180370288A1 (en)

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FR1563041A FR3045495B1 (fr) 2015-12-22 2015-12-22 Materiaux composites a base d'empilage oriente de melanges durs-mous pour le couplage mecanique
PCT/FR2016/053460 WO2017109339A1 (fr) 2015-12-22 2016-12-15 Materiaux composites a base d'empilage oriente de melanges durs-mous pour le couplage mecanique pour la fabrication de bandes de roulement de pneumatiques

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